JP2017155043A - Agrochemical composite particle and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agrochemical formulation with the effect of an agrochemical active ingredient enhanced without the need for an agricultural worker to do mixing work.SOLUTION: Particles of an agrochemical active ingredient that is solid at 25°C and carbon black particles are mixed by a mechanical particle compositing method, so that layers comprising the carbon black particles are formed on the surfaces of the agrochemical active ingredient particles.SELECTED DRAWING: None

Description

  The present invention relates to agrochemical composite particles in which solid agrochemical active ingredient particles are coated with carbon black and a method for producing the same.

  So far, various studies have been made for the purpose of enhancing the efficacy of agricultural chemical active ingredients. For example, a method is known in which the efficacy of an agrochemical active ingredient in an agrochemical formulation is enhanced by mixing and applying an agrochemical formulation and a compound having a specific polyoxyalkylene structure in the molecule (Patent Document 1). reference). However, this method requires an agricultural worker to mix the agrochemical formulation with the compound.

International Publication No. 2009/028454

  The present invention provides an agrochemical formulation in which the efficacy of an agrochemical active ingredient is enhanced without the need for an agricultural worker to perform a mixing operation.

The present invention is as follows.
[1] A step of forming a layer of carbon black particles on the particle surface of the agricultural chemical active ingredient by mixing particles of the agricultural chemical active ingredient that are solid at 25 ° C. and carbon black particles, A method for producing agrochemical composite particles, wherein the process is performed by a mechanical particle composite method.
[2] The method for producing agrochemical composite particles according to [1], wherein the particle size of the agrochemical active ingredient particles is in the range of 0.5 to 200 μm.
[3] The method of producing agrochemical composite particles according to [1] or [2], wherein the particle size of the carbon black particles is 1/5 or less of the particle size of the agrochemical active ingredient particles.
[4] A method for producing an agrochemical formulation, comprising a step of formulating the agrochemical composite particles produced by the method for producing agrochemical composite particles according to any one of [1] to [3].
[5] Agrochemical activity comprising a step of forming a layer composed of carbon black particles on the surface of the particles of the pesticidal active ingredient by mixing particles of the pesticidal active ingredient solid at 25 ° C. and carbon black particles. How to increase the potency of ingredients.
[6] Agrochemical composite particles comprising carbon black and a pesticidal active ingredient that is solid at 25 ° C., and having a layer of the carbon black particles on the surface of the pesticidal active ingredient particles.

  According to the present invention, the efficacy of a solid pesticidal active ingredient can be enhanced. The agricultural chemical formulation obtained by formulating the agrochemical composite particles of the present invention (hereinafter referred to as the present composite particles) does not require the agricultural worker to mix the potency-enhancing component at the time of application. it can. Moreover, the particle size of the present composite particle is approximately the same as the particle size of the particles of the pesticidal active ingredient before coating, and can be formulated in the same manner as the pesticidal active ingredient not coated.

It is an electron micrograph of this composite particle. (Test Example 1) It is an electron micrograph of the section of this composite particle. (Test Example 2) It is the figure which showed distribution of the thickness of the carbon black layer of this composite particle. (Test Example 2)

  The agrochemical active ingredient in the present invention is an agrochemical active ingredient that is solid at 25 ° C., and its melting point is preferably 70 ° C. or higher. Pesticide active ingredients include insecticidal active ingredients, bactericidal active ingredients, herbicidal active ingredients, insect growth control active ingredients and plant growth control active ingredients.

  Examples of the insecticidal active ingredient and insect growth controlling active ingredient include biological pesticides such as Bacillus thuringiensis; pyrethroid compounds such as deltamethrin, tralomethrin, acrinathrin, tetramethrin, and tefluthrin; propoxer, isoprocarb, xylylcarb, metolcarb, thiodicarb, XMC, carbaryl, Carbamate compounds such as pirimicarb, carbofuran, mesomil, phenoxycarb, and fenobucarb; organic phosphorus compounds such as acephate, trichlorphone, tetrachlorvinphos, dimethylvinphos, pyridafenthion, azinephosethyl, azinephosmethyl; diflubenzuron, chlorfluazuron, lufenuron, hexaful Muron, flufenoxuron, flucycloxuron, cyromazine, diafenthiuro , Hexothiazox, Novallon, teflubenzuron, triflumuron, 4-chloro-2- (2-chloro-2-methylpropyl) -5- (6-iodo-3-pyridylmethoxy) pyridazin-3 (2H) -one, 1- ( 2,6-difluorobenzoyl) -3- [2-fluoro-4- (trifluoromethyl) phenyl] urea, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (1,1 , 2,3,3,3-hexafluoropropoxy) phenyl] urea, 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazone -4-one, 1- (2,6-difluorobenzoyl) -3- [2-fluoro-4- (1,1,2,2-tetrafluoroethoxy) fe Lu] urea compounds such as urea; imidacloprid, acetamiprid, clothianidin, nitenpyram, thiamethoxam, dinotefuran, thiacloprid, and other chloronicotyl compounds; spinosads such as spinosad; diamide compounds such as fulvendiamide, chlorantraniliprole, cyantraniliprolol; Phenylpyrazole compounds such as fipronil and etiprole, tetramic acid compounds such as spirotetramat, spiromesifene and spirodiclofen, cartap, buprofezin, thiocyclam, bensultap, phenazaquin, fenpyroximate, pyridaben, hydramethylnon, chlorfenapyr, phenproximate , Pymetrozine, Pyrimidifen, Tebufenozide, Tebufenpyrad, Triazame Salts, indoxacarb, sulfuramide, milbemectin, avermectin, boric acid and paradichlorobenzene.

  Examples of such bactericidal active ingredients include pyrazolinone compounds such as fenpyrazamine; mandestrobin; benzimidazole compounds such as benomyl, carbendazim, thiabendazole, and thiophanate methyl; phenylcarbamate compounds such as dietofencarb; dicarboximide compounds such as procimidone, iprodione, and vinclozoline; Diniconazole, propenazole, epoxiconazole, tebuconazole, difenoconazole, cyproconazole, flusilazole, triazimephone and other azole compounds; metalaxyl and other acylalanine compounds; furametopyl, mepronyl, flutolanil, trifluzamide and other carboxyamide compounds; Organophosphorus compounds such as focetylaluminum and pyrazophos; Anilinopyrimidine compounds such as fludioxonil and fenpiclonyl; antibiotics such as blasticidin S, kasugamycin, polyoxin and validamycin; methoxy acrylate compounds such as azoxystrobin, cresoxime methyl, and SSF-126 Chlorothalonil, manzeb, captan, phorpet, tricyclazole, pyroxylone, probenazole, fusalide, simoxanyl, dimethomorph, famoxadone, oxolinic acid, fluazinam, ferrimzone, diclocimet, clobenazone, isovaradione, tetrachloroisophthalonitrile, thiophthalimidooxybis Phenoxyarsine, 3-iodo-2-propylbutyl carbamate, parahi Proxy benzoic acid esters, sodium dehydroacetate, potassium sorbate, orysastrobin, isotianil, triazinyl, thiuram and the like.

  Examples of such herbicidal active ingredients include: triazine compounds such as atrazine and metribudine; urea compounds such as fluometuron and isoproturon; hydroxybenzonitrile compounds such as bromoxynyl and ioxynil; 2,6-dinitro such as pendimesalin and trifluralin Allyloxyalkanoic acid compounds such as aniline compounds; 2,4-D, dicamba, fluroxypyr, mecoprop; bensulfuron methyl, methylsulfuron methyl, nicosulfuron, primsulfuron methyl, cyclosulfamuron, imazosulfuron, propyris Sulfonyl urea compounds such as ruflon and sulfosulfuron; imidazolinone compounds such as imazapyr, imazaquin and imazetapy; Bispyribac Na salt, Bisthiobac Na salt, Acifluolf Sodium salt, sulfentrazone, paraquat, flumeturum, triflusulfuron methyl, phenoxaprop-p-ethyl, diflufenican, norflurazon, isoxaflutol, glufosinate amnium salt, glyphosate, bentazone, mefenacet, Propanyl, fluthiamide, full microlac pentyl, flumioxazin, bromobutide and the like can be mentioned.

  Examples of such plant growth control active ingredients include maleic hydrazide, chlormecat, etephone, gibberellin, mepicut chloride, thiazuron, inavenfide, paclobutrazol, uniconazole.

  As the pesticidal active ingredient in the present invention, fenpyrazamine, flumioxazin, clothianidin and Bacillus thuringiensis are preferable.

The particle size of the particles of the pesticidal active ingredient in the present invention is in the range of 0.5 to 200 μm. However, the particle size of the particles of the pesticidal active ingredient is determined according to the form (form) of the preparation to be selected when the composite particles are formulated, and in the case of the dosage form (for example, powder and granules) to be applied as it is, Usually in the range of 1 to 200 μm, preferably 3 to 100 μm, more preferably 5 to 50 μm. In the case of a dosage form (for example, an aqueous suspension preparation and a wettable powder) to be applied by mixing with water, usually 0.5 It is -100 micrometers, Preferably it is 1-50 micrometers, More preferably, it is the range of 1-25 micrometers. In the present invention, the particle size of the pesticidal active ingredient particles means a particle size that is 50% in cumulative frequency in the volume-based frequency distribution, and is obtained by wet measurement using a laser diffraction particle size distribution measuring device. it can. More specifically, the particles of the pesticidal active ingredient are dispersed in water and the measurement is performed using the apparatus. An example of such a laser diffraction type particle size distribution measuring apparatus is Mastersizer 2000 manufactured by Malvern.
In the present invention, the pesticidal active ingredient powder pulverized using a pulverizer as necessary is used as the pesticidal active ingredient particles. Examples of the pulverizer include a jet mill and a centrifugal pulverizer.

The carbon black in the present invention is carbon fine particles having a particle size of 500 nm or less, and is generally known as a black pigment and an additive for rubber. The particle size of the carbon black particles in the present invention is usually 1/5 or less, preferably 1/10 or less, of the particle size of the agrochemical active ingredient particles. In the present invention, it is preferable to use carbon black having a particle size of 100 nm or less. In the present invention, the particle diameter of carbon black particles means the number average diameter. For example, an electron microscope image of carbon black is analyzed using commercially available software such as WINROOF (manufactured by Mitani Corporation), and 100 particles are obtained. It can obtain | require by calculating the average value of the particle size of.
In the present invention, commercially available carbon black powder can be used as the carbon black particles. Examples of such commercially available carbon black powder include Toka Black # 8500 / F and Toka Black # 7100 / F manufactured by Tokai Carbon Co., Ltd.

The production method of the present composite particle (hereinafter referred to as the present composite particle production method) will be described below.
The present composite particle production method comprises a step of forming a layer composed of carbon black particles on the surface of particles of an agrochemical active ingredient by mixing particles of the agrochemical active ingredient that are solid at 25 ° C. and carbon black particles ( Hereinafter, this process is described). This step is performed by a mechanical particle composite method. The mechanical particle compositing method is a method for producing composite particles using a machine such as a pulverizer and a mixer, and is different from the core particles (hereinafter referred to as mother particles) and the mother particles. By adding mechanical energy such as compression, shearing, friction and impact to a mixture of a substance and particles smaller than the mother particles (hereinafter referred to as child particles), the mother particles can be produced without using a binder. It is known as a technique for producing composite particles by coating with a large number of child particles. The technology is described in a large number of documents, such as “Next Generation Fine Particle Coating Technology for Pharmaceutical Formulation Development” (supervised by Hideki Ichikawa, CMC Publishing Co., Ltd., December 3, 2012). P.111-118). The mechanical particle composite method can be performed by using a commercially available particle composite apparatus. Examples of such commercially available particle compositing devices include a hybridization system (registered trademark) manufactured by Nara Machinery Co., Ltd., and a high-speed impact dry particle compositing device such as Kryptron manufactured by Earth Technica Co., Ltd. Mechanofusion (registered trademark) manufactured by Hosokawa Micron Co., Ltd., Nobilta (registered trademark) NOB manufactured by Hosokawa Micron Co., Ltd., which is an apparatus described in JP-A-2005-270955, Examples include a compression shear type dry particle compounding apparatus. This step is preferably performed using a nobilta.

In this step, agrochemical active ingredient powder is used as the mother particle, and carbon black powder is used as the child particle. When the compound obtained by blending the agrochemical active ingredient powder and the carbon black powder in a predetermined ratio is mixed with the particle compounding device, the carbon black particles adhere to the surface of the agrochemical active ingredient particles, and the carbon black particles A layer is formed. The weight ratio of the pesticidal active ingredient powder to the carbon black powder may vary depending on the particle size and true specific gravity of the pesticidal active ingredient particles and the particle size and true specific gravity of the carbon black, but is usually from 4:96 to 99.7: 0. 3, preferably 16:84 to 99.4: 0.6, more preferably 25:75 to 99: 1. In this step, the entire amount of the pesticidal active ingredient powder and the carbon black powder may be charged all at once into the mixing vessel of the particle compounding apparatus, the total amount of the pesticidal active ingredient powder is charged, and the carbon black powder is divided. You may throw it in. When the whole amount of the pesticidal active ingredient powder and the carbon black powder is put into the mixing container of the particle compounding apparatus at a time, the pesticidal active ingredient powder and the carbon black powder are put into the mixing container of the particle combining apparatus, respectively. A mixture obtained by previously mixing the agrochemical active ingredient powder and the carbon black powder using a mixer such as Nautamixer (registered trademark) manufactured by Hosokawa Micron Corporation may be added. The total amount of the pesticidal active ingredient powder and the carbon black powder is charged into the mixing container of the particle compounding device, and then the particle compounding device is operated and mixed to obtain the present composite particles.
When the whole amount of the agrochemical active ingredient powder is charged into the mixing container of the particle compounding apparatus and the carbon black powder is divided and added, first, the total amount of the agrochemical active ingredient powder and carbon black are mixed into the mixing container of the particle compounding apparatus. A part of the powder is charged and the particle compounding apparatus is operated and mixed to perform a step of obtaining composite particles (hereinafter referred to as step 1). Next, a step of adding a part of the carbon black powder, operating the particle compounding apparatus, mixing the composite particles obtained in step 1 and the carbon black powder, and coating the composite particles with carbon black (hereinafter referred to as “carbon black”) The composite particles can be obtained by repeatedly performing the step 2). Further, after carrying out step 1, a part of the obtained composite particles can be taken out from the apparatus, and the same amount of carbon black as that of the taken out composite particles can be added in step 2.

  The mixing strength at the time of mixing with the particle compounding apparatus is usually in the range of 0.005 to 0.25 kW / g, preferably 0.01 to 0.05 kW / g. In the present invention, the mixing strength is a value obtained by dividing the power (kW) of the particle compounding apparatus at the time of mixing by the amount of powder (g) charged into the mixing container of the particle compounding apparatus. . Moreover, mixing time is 0.5 to 20 minutes normally, Preferably it is the range of 3 to 15 minutes.

  The value of the specific surface area of the composite particles is usually 1/2 to 40 times, preferably 1/4 of the value of the specific surface area of the mixture obtained by simply mixing the agrochemical active ingredient powder and the carbon black powder. It is in a range of ˜25. In the present invention, the specific surface area means a value determined by the BET method. Specifically, using BELPREP-VAC II (manufactured by Nippon BEL), the surface of the powder particles pre-treated by vacuum degassing at approximately 25 ° C. for approximately 12 hours is applied to BELSORP-mini (manufactured by Nippon BEL). The adsorption / desorption isotherm obtained by measurement using the constant volume method of the nitrogen adsorption method is analyzed by the BET method (analysis method using the BET equation).

FIG. 2 is an electron micrograph of a cross section of the present composite particle. As shown in FIG. 2, the present composite particle has a layer composed of a number of carbon black particles (hereinafter referred to as a carbon black layer) on the surface of one agrochemical active ingredient particle. The particle surface of the agrochemical active ingredient does not necessarily have to be entirely covered with carbon black. In the present invention, 50% or more of the particle surface of the agrochemical active ingredient is preferably covered with carbon black, and more preferably 100%. Further, it is preferable that 100% of the particle surface of the pesticidal active ingredient is covered and the carbon black layer is thick. The average thickness of the carbon black layer is usually in the range of 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 20 μm.
The average thickness of the carbon black layer is determined as follows. The composite particles are embedded in a resin, a cross section is prepared using a microtome, and in the digital image of the cross section observed using a scanning electron microscope, the particles of the pesticidal active ingredient are gray, the carbon black layer is white, After the embedding resin part outside the composite particles is trinated to black, the shortest distance from the starting point to the pixel at the boundary between the white part and the black part is imaged starting from the pixel at the boundary between the white part and the gray part Obtained by analysis, this operation is performed at all starting points. A number average value of distances of several thousand to several tens of thousands of points obtained by performing the same image analysis on about several tens to 100 of the present composite particles is an average thickness of the carbon black layer.
Moreover, the particle size of this composite particle is 1.0-1.5 times the particle size of the particle | grains of an agrochemical active ingredient. The composite particles preferably have a fineness of 2% or less. In the present invention, the fineness is a value determined by the following method. First, the preparation containing the composite particles is diluted 100 times with ion-exchanged water, and the dispersion obtained by stirring with a magnetic stirrer is passed through a sieve having an opening of 300 μm, and tap water until the amount of the residue becomes constant. Wash with. Next, the residue on the sieve is transferred to a petri dish, the water is evaporated, and the weight of the residue is weighed. The ratio (%) of the residue weight to the weight of the composite particles used in the test is a result of the fineness.

  The carbon black content in the composite particles is usually 0.3 to 96% by weight, preferably 0.6 to 84% by weight, and more preferably 1 to 75% by weight. Further, the weight ratio of the pesticidal active ingredient to carbon black in the present composite particle may vary depending on the particle size and true specific gravity of the pesticidal active ingredient particle and the particle size and true specific gravity of the carbon black, but usually 4:96 to 99.99. It is in the range of 7: 0.3, preferably 16:84 to 99.4: 0.6, more preferably 25:75 to 99: 1.

The manufacturing method of the agrochemical formulation of this invention has the process of formulating this composite particle. The composite particles can be formulated in the same manner as solid agrochemical active ingredients that are not complexed. Moreover, since it is adjusted to a desired particle size at the time of compounding, it is not necessary to grind at the time of formulation. Formulation is performed by a known method. This composite particle is mixed with formulation aids such as solid inert carriers, binders and surfactants, and wettable powder, powder, DL (driftless) powder, granule, fine granule, fine granule F, granule It can be formulated into solid preparations such as wettable powders, jumbo preparations and tablets. In addition, the composite particles, a dispersion medium such as water and an organic solvent, and a formulation aid such as a surfactant may be mixed to prepare a liquid formulation such as an aqueous suspension formulation, an aqueous emulsion formulation, and an oil flowable. it can.
The preparation obtained by formulating the composite particles can be used in the same manner as conventional agricultural chemical preparations, and can be applied to places such as paddy fields, upland fields, orchards, turflands, and non-agricultural lands. If necessary, the preparation is mixed with water and sprayed on the plant growing in the place or the soil in the place. Examples of the method for spraying the diluted solution obtained by mixing the preparation with water include soil surface spraying and foliage spraying using a known spraying machine. The diluted solution can also be used for seed treatment, seedling box treatment and the like.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited only to these examples.

Reference production example 1
By using a vertical jet mill (JOM-0101 type jet pulverizer, manufactured by Seishin Enterprise Co., Ltd.) and pulverizing fenpyrazamine with dry pulverization while changing the air pressure, the particle sizes were 2.4 μm, 5.0 μm, 7.8 μm and A fenpyrazamine powder having a size of 8.3 μm was obtained (hereinafter, referred to as fenpyrazamine powder A, fenpyrazamine powder B, fenpyrazamine powder C, and fenpyrazamine powder D).

Production Example 1
9.6 g of fenpyrazamine powder A and 2.4 g of carbon black powder (Toka Black 8500 / F, manufactured by Tokai Carbon Co., Ltd.) are charged into a mixing container of a particle composite device (Nobilta NOB-MINI, manufactured by Hosokawa Micron Co., Ltd.) The mixture was mixed at a power of 330 to 390 W for 10 minutes to obtain composite particles 1a. 2.0 g of composite particles 1a were taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) was added, and mixed for 10 minutes at a power of 280 to 290 W to obtain composite particles 1b. 2.0 g of composite particles 1b are taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) is added and mixed for 10 minutes at a power of 270 to 280 W, and the agrochemical composite particles (1) of the present invention (hereinafter, Agrochemical composite particles (denoted as (1)) were obtained.

Production Example 2
Fenpyrazamine powder A92g and carbon black powder (same as above) 48g are put into a mixing vessel of a particle compounding device (Nobilta NOB-130, manufactured by Hosokawa Micron Corporation), mixed for 20 minutes at a power of 3.0 kW, and composite particles 2a was obtained. 40 g of composite particles 2a were taken out from the mixing container, 40 g of carbon black powder (the same as described above) was added, and mixed for 20 minutes at a power of 3.0 kW to obtain composite particles 2b. 40 g of the composite particle 2b is taken out from the mixing container, 40 g of carbon black powder (the same as described above) is added, and mixed for 40 minutes at a power of 3.0 kW. 2)) was obtained.

Production Example 3
10 g of agricultural chemical composite particles (2) and 2.0 g of carbon black powder (same as above) are put into a mixing vessel of a particle composite device (Nobilta NOB-MINI, manufactured by Hosokawa Micron Co., Ltd.). Mixed for 3 minutes to obtain composite particles 3a. 2.0 g of composite particles 3a are taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) is added, mixed for 10 minutes at a power of 280 to 310 W, and the agricultural chemical composite particles (3) of the present invention (hereinafter, Agrochemical composite particles (denoted as (3)) were obtained.

Production Example 4
10 g of agricultural chemical composite particles (3) and 2.0 g of carbon black powder (same as above) are put into a mixing vessel of a particle composite device (same as above), and mixed for 10 minutes at a power of 210 to 250 W. The agrochemical composite particles (4) (hereinafter referred to as agrochemical composite particles (4)) were obtained.

Production Example 5
Fenpyrazamine powder C 11.4 g and carbon black powder (same as above) 0.6 g are put into a mixing vessel of a particle compounding device (same as above) and mixed for 10 minutes at a power of 200 to 320 W. Obtained. 0.6 g of the composite particle 5a is taken out from the mixing container, 0.6 g of carbon black powder (the same as described above) is added, and mixed for 10 minutes at a power of 190 to 220 W. The agricultural chemical composite particle (5) of the present invention (hereinafter, Agricultural chemical composite particles (5)) were obtained.

Production Example 6
9.6 g of fenpyrazamine powder D and 2.4 g of carbon black powder (same as above) are put into a mixing vessel of a particle compounding device (same as above) and mixed for 10 minutes at a power of 266 to 319 W to obtain composite particles 6a. Obtained. 2.0 g of composite particles 6a were taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) was added, and mixed for 10 minutes at a power of 220 to 231 W to obtain composite particles 6b. Taking out 2.0 g of composite particles 6b from the mixing container, adding 2.0 g of carbon black powder (the same as described above), mixing for 10 minutes at a power of 202 to 267 W, the agrochemical composite particles (6) of the present invention (hereinafter, Agricultural chemical composite particles (6)) were obtained.

Production Example 7
Pesticide composite particles (6) 10 g and carbon black powder (same as above) 2.0 g are put into a mixing vessel of a particle composite device (same as above) and mixed for 10 minutes at a power of 231 to 274 W. 7a was obtained. 2.0 g of composite particles 7a were taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) was added, and mixed for 10 minutes at a power of 148 to 235 W to obtain composite particles 7b. 2.0 g of the composite particle 7b is taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) is added, and mixed for 10 minutes at a power of 78 to 122 W. The agricultural chemical composite particle (7) of the present invention (hereinafter, Agricultural chemical composite particles (7)) were obtained.

Production Example 8
Flumioxazin was dry-ground using a vertical jet mill (the same as described above) to obtain flumioxazin powder having a particle size of 3.0 μm. 10 g of the flumioxazin powder and 2 g of carbon black powder (same as above) were put into a mixing vessel of a particle composite device (same as above) and mixed for 10 minutes at a power of 270 to 300 W to obtain composite particles 8a. . 2 g of composite particles 8a were taken out from the mixing container, 2 g of carbon black powder (the same as described above) was added, and mixed for 10 minutes at a power of 240 to 270 W to obtain composite particles 8b. 2 g of composite particles 8b are taken out from the mixing container, 2 g of carbon black powder (the same as described above) is added, and mixed for 10 minutes at a power of 210 to 260 W. 8)) was obtained.

Production Example 9
9.6 g of fenpyrazamine powder B and 2.4 g of carbon black powder (same as above) are put into a mixing vessel of a particle compounding device (same as above), mixed for 10 minutes at a power of 239 to 328 W, and composite particles 9a are mixed. Obtained. 2.0 g of composite particles 9a are taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) is added, mixed for 10 minutes at a power of 148 to 257 W, and the agrochemical composite particles (9) of the present invention (hereinafter, Agricultural chemical composite particles (9)) were obtained.

Production Example 10
Clothianidin was dry-ground using a vertical jet mill (the same as described above) to obtain clothianidin powder having a particle size of 3.5 μm. 9.6 g of the clothianidin powder and 2.4 g of carbon black powder (same as above) are put into a mixing vessel of a particle composite device (same as above) and mixed for 10 minutes at a power of 248 to 274 W to obtain composite particles 10a. Got. 2.0 g of composite particles 10a are taken out from the mixing container, 2.0 g of carbon black powder (the same as described above) is added, and mixed for 10 minutes at a power of 257 W. Particles (denoted as (10)).

Production Example 11
Bacillus thuringiensis (BACILLUS THURINGIENSIS, hereinafter referred to as BT) was dry pulverized using a vertical jet mill (the same as described above) to obtain a BT powder having a particle size of 21 μm. 9.6 g of the BT powder and 2.4 g of carbon black powder (same as above) are put into a mixing vessel of a particle compounding device (same as above) and mixed for 10 minutes at a power of 187 to 231 W. Agrochemical composite particles (11) (hereinafter referred to as agrochemical composite particles (11)) were obtained.

Formulation Example 1
Magnesium aluminum silicate (trade name: VEEGUM (registered trademark) R, manufactured by Vanderbilt) (0.16 parts by weight) was added to 5.68 parts by weight of deionized water, and the mixture was stirred at room temperature for 15 minutes. Xanthan gum (trade name: KELZAN (registered trademark) S, CP Kelco) 0.08 part by weight and 2 parts by weight of propylene glycol were added and mixed to obtain a mixture. The dispersion obtained by stirring the mixture at 60 ° C. for 60 minutes was cooled to room temperature, and 0.08 part by weight of a preservative (trade name: Proxel GXL, Lonza) was added to the dispersion. A viscosity adjusting liquid was obtained. 8 parts by weight of the viscosity adjusting liquid, 38.8 parts by weight of the agricultural chemical composite particles (2), 5 parts by weight of sodium lignin sulfonate (trade name: REAX (registered trademark) 85A, manufactured by Meadwestvaco), an antifoaming agent (trade name: 0.2 parts by weight of KS-530 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 48 parts by weight of deionized water were mixed to obtain an aqueous suspension preparation (1).

Formulation Example 2
8 parts by weight of the viscosity adjusting liquid obtained in Formulation Example 1, 27.6 parts by weight of agricultural chemical composite particles (4), 2.5 parts by weight of sodium lignin sulfonate (same as above), 0 defoamer (same as above) 0 2 parts by weight and 61.7 parts by weight of deionized water were mixed to obtain an aqueous suspension preparation (2).

Formulation Example 3
8 parts by weight of the viscosity adjusting liquid obtained in Formulation Example 1, 27.6 parts by weight of agricultural chemical composite particles (5), 2.5 parts by weight of sodium lignin sulfonate (same as above), 0 defoamer (same as above) 0 2 parts by weight and 61.7 parts by weight of deionized water were mixed to obtain an aqueous suspension preparation (3).

Formulation Example 4
17.3 parts by weight of agricultural chemical composite particles (2) and 12.7 parts by weight of liquid paraffin (trade name: Moresco White P-40, manufactured by MORESCO Co., Ltd.) are mixed to obtain a suspension of the agricultural chemical composite particles (2). Got. 30 parts by weight of the suspension was added to 33 parts by weight of an aqueous solution of 5% by weight polyvinyl alcohol (trade name: Gohsenol GH-17, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and a rotor stator type homogenizer (trade name: POLYTRON (registered trademark)). By stirring using PT6100 (manufactured by KINEMATICA), the suspension is emulsified in an aqueous polyvinyl alcohol solution, and an emulsion of liquid paraffin (hereinafter referred to as emulsion (hereinafter referred to as emulsion)) containing agrochemical composite particles (2). 2)) was obtained.
To 14.2 parts by weight of deionized water, 0.4 parts by weight of magnesium aluminum silicate (same as above) was added and stirred at room temperature for 15 minutes. Xanthan gum (same as above) 0.2 parts by weight and propylene glycol 5 parts by weight were added and mixed to obtain a mixture. The dispersion obtained by stirring the mixture at 60 ° C. for 60 minutes was cooled to room temperature, and then 0.2 parts by weight of an antiseptic (the same as described above) was added to the dispersion to obtain a viscosity adjusting liquid. . 20 parts by weight of the viscosity adjusting liquid, 17 parts by weight of deionized water and 63 parts by weight of the emulsion (2) were mixed to obtain an aqueous emulsion preparation (1). The average particle diameter of the droplets in the aqueous emulsion preparation (1) was 26.0 μm.

Formulation Example 5
Pesticide composite particles (3) 55.8 parts by weight, potassium polycarboxylate (trade name: GERAPON (registered trademark) SC / 213, manufactured by Rhodia) 5 parts by weight, potassium dihydrogen phosphate 4.0 parts by weight, antifoaming An aqueous suspension was obtained by mixing 2.5 parts by weight of the agent (same as above), 32.7 parts by weight of sodium lignin sulfonate (same as above) and 150 parts by weight of deionized water until uniform. The aqueous suspension was spray-dried using a spray dryer (model SD-1, manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a granular wettable powder (1).

Formulation Example 6
Agrochemical composite particles (3) 55.8 parts by weight, sodium lauryl sulfate (trade name: EMAL 10PT, manufactured by Kao Corporation), sodium salt of a special aromatic sulfonic acid formalin condensate (trade name: demole SNB, Kao) Co., Ltd.) 10 parts by weight, wax (product name: Katsuyama clay S, manufactured by Katsuyama Mine) 30.2 parts by weight and deionized water 25 parts by weight using a mortar to obtain a kneaded product It was. The kneaded product was granulated using dome gran (extruded diameter φ0.7 mm), and the obtained granulated product was dried with a drier and then granulated to obtain a granulated wettable powder (2).

Formulation Example 7
Agrochemical composite particles (4) 67.8 parts by weight, sodium alkylnaphthalene sulfonate (Morwet (registered trademark) EFW, manufactured by Akzo Nobel) 3 parts by weight, formalin condensate of sodium naphthalene sulfonate (Morwet (registered trademark) D-425 10 parts by weight of Akzo Nobel) and 19.2 parts by weight of wax (same as above) were mixed using a mortar to obtain wettable powder (1).

Formulation Example 8
Pesticide composite particles (9) 33 parts by weight, sodium alkylnaphthalene sulfonate (same as above) 3 parts, sodium naphthalene sulphonate formalin condensate (same as above) and wax stone (same as above) 54 parts Parts were mixed using a juice mixer to obtain a wettable powder (2).

Formulation Example 9
Pesticide composite particles (10) 31 parts by weight, sodium alkylnaphthalene sulfonate (same as above) 4 parts, sodium naphthalene sulfonate formalin condensate (same as above) and wax (same as above) 50 parts Parts were mixed using a juice mixer to obtain a wettable powder (3).

Formulation Example 10
Agrochemical composite particles (11) 5 parts by weight, liquid paraffin (trade name: Doreles C, Sankyo Co., Ltd.) 0.13 parts by weight, wet process silica (trade name: Tokseal NP, manufactured by Tokuyama Siam Silica) 0.07 part by weight, 94.8 parts by weight of dry clay (trade name: DL clay, Hayashi Kasei Co., Ltd.) was mixed using a juice mixer to obtain a powder (1).

Formulation Example 11
Pesticide composite particles (8) 35 parts by weight, sodium alkylnaphthalene sulfonate (same as above) 5 parts, sodium naphthalene sulfonate formalin condensate (same as above) and wax (same as above) 50 parts Parts were mixed using a mortar to obtain a wettable powder (4).

Formulation Example 12
Agrochemical composite particles (6) 66.3 parts by weight, sodium alkylnaphthalene sulfonate (Morwet (registered trademark) EFW, manufactured by Akzo Nobel) 3 parts by weight, formalin condensate of sodium naphthalene sulfonate (Morwet (registered trademark) D-425 10 parts by weight of Akzo Nobel) and 20.7 parts by weight of wax (same as above) were mixed using a mortar to obtain wettable powder (5).

Reference production example 2
Fenpyrazamine powder D52 parts by weight and carbon black powder (same as above) 48 parts by weight are put in a polyethylene bag, and the polyethylene bag is shaken vigorously to mix, and a comparative mixture of fenpyrazamine and carbon black (1) (below) A comparative mixture (1)).

Reference production example 3
Add 31 parts by weight of fenpyrazamine powder D and 69 parts by weight of carbon black powder (same as described above) into a polyethylene bag, shake the polyethylene bag vigorously and mix to obtain a mixture of fenpyrazamine and carbon black for comparison (2) (below) A comparative mixture (2)).

Reference formulation example 1
51.2 parts by weight of fenpyrazamine having a particle size of 150 μm, 5 parts by weight of potassium polycarboxylate (same as above), sodium lignin sulfonate (trade name: REAX® 80D, manufactured by Meadwestvaco), 37.3 parts by weight After mixing 0.5 part by weight of a foaming agent (same as above) and deionized water (weight ratio 1: 4) and 117 parts by weight of deionized water, a horizontal bead mill (trade name: DYNO (registered trademark) − MILL KDL, manufactured by Willy A Bachofen) was wet-pulverized to obtain a fenpyrazamine suspension. On the other hand, 4 parts by weight of potassium dihydrogen phosphate was dissolved in 23 parts by weight of deionized water to obtain an aqueous potassium dihydrogen phosphate solution. The fenpyrazamine suspension was mixed with 12 parts by weight of the aqueous potassium dihydrogen phosphate solution and antifoaming agent (same as above) and deionized water (weight ratio 1: 4) to obtain an aqueous suspension. . The aqueous suspension is sprayed using a fluidized bed granulator (STREA-1, manufactured by Paulek), and granulated by a method of continuously performing fluidized bed granulation following spray granulation. Granule wettable powder (1) (hereinafter referred to as comparative granule wettable powder (1)) was obtained.

Reference formulation example 2
20 parts by weight of fenpyrazamine powder B, 13 parts by weight of carbon black powder (same as above), 3 parts by weight of sodium alkylnaphthalene sulfonate (same as above), 10 parts by weight of formalin condensate of sodium naphthalene sulfonate (same as above) and wax 54 parts by weight of stone (the same as described above) was mixed using a juice mixer to obtain a comparative wettable powder (1) (hereinafter referred to as comparative wettable powder (1)).

Reference formulation example 3
Juice mixer with 21 parts by weight of fenpyrazamine powder B, 5 parts by weight of sodium alkylnaphthalene sulfonate (same as above), 15 parts by weight of a formalin condensate of sodium naphthalene sulfonate (same as above) and 60 parts by weight of rholite (same as above) To obtain a comparative wettable powder (2) (hereinafter referred to as comparative wettable powder (2)).

Reference formulation example 4
20 parts by weight of clothianidin powder (particle size 3.5 μm) obtained in Production Example 10, 11 parts by weight of carbon black powder (same as above), 5 parts by weight of sodium alkylnaphthalene sulfonate (same as above), sodium naphthalene sulfonate 15 parts by weight of a formalin condensate (same as above) and 50 parts by weight of a wax (same as above) were mixed using a juice mixer, and a comparative wettable powder (3) (hereinafter referred to as comparative wettable powder (3 )).

Reference formulation example 5
1 part by weight of BT powder obtained in Production Example 11, 4 parts by weight of carbon black powder (same as above), 0.13 part by weight of liquid paraffin (same as described in Formulation Example 10), wet method silica (as described above) 0.068 parts by weight of the same and 94.8 parts by weight of dry clay (same as above) are mixed using a juice mixer to obtain a comparative powder (1) (hereinafter referred to as comparative powder (1)). It was.

Test example 1
The agricultural chemical composite particles (1) were observed using a scanning electron microscope (model number: S-5500, manufactured by Hitachi, Ltd.). An electron micrograph of the pesticide composite particles (1) is shown in FIG.

Test example 2
Agrochemical composite particles (1) and (4) were each embedded in an epoxy resin, and a particle cross section was prepared using an ultramicrotome (model number: Leica EM UC7, manufactured by Leica Microsystems) and a diamond knife. The particle cross section was observed using a scanning electron microscope (same as above). An electron micrograph of the cross section of the pesticide composite particle (4) is shown in FIG. Further, in the observed digital image of the cross section of the particles, the pesticidal composite particles (1) have 148 particles and the pesticidal composite particles (4) have 75 particles of the pesticidal active ingredient in gray, the carbon black layer in white, After the embedding resin portion outside the composite particle is trinized to black, the pixel at the boundary between the white portion and the gray portion of each particle is used as the starting point, and the pixel from the starting point to the pixel at the boundary between the white portion and the black portion is used. The shortest distance was determined by image analysis, and this operation was performed at all starting points. Agricultural chemical compound measured by obtaining the number average of 36188 points (agricultural compound particles (1)) and 25668 points (agrochemical compound particles (4)) obtained by performing the same image analysis on all particles. The thickness distribution of each carbon black layer of the particles (1) and (4) is shown in FIG.

Test example 3
Pesticide composite particles (6) and (7) and comparative mixtures (1) and (2) were vacuum degassed at about 25 ° C for about 12 hours using BELPREP-VAC II (manufactured by BEL, Japan), respectively. After pretreatment, the specific surface area was calculated by the BET method from the adsorption / desorption isotherm measured by the constant volume method of the nitrogen adsorption method using BELSORP-mini (manufactured by Nippon BEL). The results are shown in Table 1.

Test example 4
0.2 g of wettable powder (5) was charged into a 100 mL beaker containing 20 ml of ion-exchanged water, and then dispersed by stirring with a magnetic stirrer. The dispersion was passed through a sieve having an opening of 300 μm, and then washed with tap water until the amount of the residue became constant. The residue on the sieve was transferred to a petri dish, the water was evaporated, and the weight of the residue was weighed. The amount of the residue was 0.02% of the amount of the agrochemical composite particles contained in the wettable powder used in the test .

Test Example 5
The aqueous suspension preparations (1) and (2) and the comparative granule wettable powder (1) were mixed with water so that the concentration of the active ingredient was 2500 ppm, respectively, to obtain test solutions. Each of the test liquids was sprayed on the cucumber leaf surface using a traveling sprayer set to a spray liquid amount of 100 L / ha. Then, the cucumber leaves were air-dried. Next, a rain treatment was performed on the cucumbers using an artificial rain apparatus (manufactured by Daiki) so that the total rainfall was 60 mm. Then, the cucumber leaves were air-dried. Next, a mycelia-containing potato broth agar medium of gray mold disease was inoculated on the leaf surface. This is the treatment area.
Further, the same operation as in the treatment section was performed except that the test solution was not sprayed. Let this be an untreated zone.
Thereafter, the cucumber was placed at 20 ° C. under high humidity for 4 days, and then the diameter of the lesion formed on the leaf surface of the cucumber was measured. As a result, lesions with a diameter of 90% of the untreated area were observed on the foliage sprayed with the comparative granule wettable powder (1), but the foliage sprayed with the aqueous suspension preparation (1) or (2) No lesions were found.

Test Example 6
Aqueous suspension preparations (1), (2) and (3) and comparative granule wettable powder (1) were mixed with water so that the concentration of the active ingredient was 50 ppm, respectively, to obtain test solutions. The test liquid was sprayed on the cucumber leaf surface using a traveling sprayer set at a spray liquid amount of 1000 L / ha. From the day after spraying, after exposure to sunlight for 6 days on a sunny day, the mycelia-containing potato broth agar medium of gray mold disease was inoculated on the leaf surface. This is the treatment area.
Further, the same operation as in the treatment section was performed except that the test solution was not sprayed. Let this be an untreated zone.
Then, after placing the cucumber under high humidity for 8 days, the diameter of the lesion formed on the cucumber leaf surface was measured. As a result, on the foliage sprayed with the comparative granule wettable powder (1), a lesion having a diameter of 37% of the untreated group was observed, but the aqueous suspension preparation (1), (2) or (3) No lesions were observed on the sprayed leaves.

Test Example 7
The wettable powder (2) and the comparative wettable powder (1) and (2) were mixed with water so that the concentration of the active ingredient was 50 ppm, respectively, to obtain test solutions. 50 mL of the test solution was sprayed on a cucumber leaf surface with a spray gun. After management in the greenhouse for one week from the day after spraying, potato broth agar medium containing mycorrhizal fungi was inoculated on the leaves. This is the treatment area.
Further, the same operation as in the treatment section was performed except that the test solution was not sprayed. Let this be an untreated zone.
Then, after placing the cucumber under high humidity for 3 days, the diameter of the lesion formed on the cucumber leaf surface was measured. As a result, lesions with diameters of 18% and 61% in the untreated group were observed on the foliage sprayed with the comparative wettable powder (1) and (2), respectively. No lesions were observed on the sprayed leaves.

Test Example 8
The wettable powder (2) and the comparative wettable powders (1) and (2) were mixed with water so that the concentration of the active ingredient was 100 ppm, respectively, to obtain test solutions. 50 mL of the test solution was sprayed on a cucumber leaf surface with a spray gun. Then, the cucumber leaves were air-dried. Next, the cucumber was subjected to a rain treatment so that the total rainfall was 10 mm using an artificial rain apparatus, and then the leaf surface of the cucumber was air-dried. Next, a potato broth agar medium containing mycelia of mycorrhizal fungi was inoculated on the leaf surface. This is the treatment area.
Further, the same operation as in the treatment section was performed except that the test solution was not sprayed. Let this be an untreated zone.
Then, after placing the cucumber under high humidity for 3 days, the diameter of the lesion formed on the cucumber leaf surface was measured. As a result, lesions with diameters of 20% and 29% in the untreated group were observed on the foliage sprayed with the comparative wettable powder (1) and (2), respectively. 10% of lesions in the untreated group were observed on the sprayed leaves.

Test Example 9
Tested by mixing wettable powder (3) and comparative wettable powder (3) with a spreading agent (trade name: Cyndine) 5000 times diluted solution (using ion-exchanged water) so that the concentration of the active ingredient is 1000 ppm. Each liquid was obtained. 25 mL of the test solution was sprayed on 6 pot planted cabbages using a spray gun. It was managed in the glass house after the spraying process. This is the treatment area.
Further, the same operation as in the treatment section was performed except that the test solution was not sprayed. Let this be an untreated zone.
After nine weeks, I counted all parasites. As a result, infestation of 201 heads in the non-treated area and 159 heads in the treated area sprayed with the comparative wettable powder (3) was observed, whereas in the treated area sprayed with the wettable powder (3), 75 heads were observed. Parasitism was observed.

Test Example 10
3120 mg each of the powder (1) and the comparative powder (1) was sprayed on 6 pot planted cabbages using a manual small powder sprayer. It was managed in the glass house after the spraying process. This is the treatment area.
In addition, the same operation as in the treatment section was performed except that no chemical was sprayed. Let this be an untreated zone.
Four weeks later, one leaf of each strain was cut out and housed in a 500 ml plastic cup with 10 second-ordered larvae, and after 7 days the rate of dead moth (including poisoning) was examined. As a result, the ratio of dead insects (including poisoning) was 10% in the untreated area and 37% in the treated area sprayed with the comparative powder (1), whereas 83% in the treated area sprayed with the powder (1). Met.

  The composite particles can be easily formulated. The agricultural chemical formulation obtained by formulating the composite particles can improve the rain resistance and residual effect even if the agricultural worker does not mix the efficacy enhancing component at the time of application.

Claims (6)

A step of forming a layer of carbon black particles on the surface of the particles of the pesticidal active ingredient by mixing particles of the pesticidal active ingredient solid with carbon black particles at 25 ° C., A method for producing agrochemical composite particles performed by a mechanical particle composite method. The manufacturing method of the agrochemical composite particle of Claim 1 whose particle size of the particle | grains of an agrochemical active ingredient is the range of 0.5-200 micrometers. The method for producing agrochemical composite particles according to claim 1 or 2, wherein the particle size of the carbon black particles is 1/5 or less of the particle size of the particles of the agrochemical active ingredient. The manufacturing method of an agrochemical formulation which has the process of formulating the agrochemical composite particle manufactured by the manufacturing method of the agrochemical composite particle of any one of Claims 1-3. The efficacy of an agrochemical active ingredient having a step of forming a layer composed of carbon black particles on the surface of the agrochemical active ingredient particle by mixing particles of the agrochemical active ingredient solid at 25 ° C. and carbon black particles. Enhancement method. A pesticidal composite particle comprising carbon black and a pesticidal active ingredient that is solid at 25 ° C., and having a layer made of the carbon black particles on the particle surface of the pesticidal active ingredient.